US4228307A - Removal of bromine from acetic acid - Google Patents
Removal of bromine from acetic acid Download PDFInfo
- Publication number
- US4228307A US4228307A US05/970,226 US97022678A US4228307A US 4228307 A US4228307 A US 4228307A US 97022678 A US97022678 A US 97022678A US 4228307 A US4228307 A US 4228307A
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- US
- United States
- Prior art keywords
- acetic acid
- bromine
- absorbant
- contaminated
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 152
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 39
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 12
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 claims abstract 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012808 vapor phase Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract 1
- 229960000583 acetic acid Drugs 0.000 description 41
- 235000011054 acetic acid Nutrition 0.000 description 40
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000001273 butane Substances 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- -1 aromatic carboxylic acids Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- DJTZIDSZSYWGKR-UHFFFAOYSA-N acetic acid tetrahydrate Chemical class O.O.O.O.CC(O)=O DJTZIDSZSYWGKR-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910001503 inorganic bromide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Definitions
- This invention relates to the removal of bromine from acetic acid and more specifically pertains to the removal of bromine from acetic acid obtained by the catalytic liquid phase oxidation of butane in the presence of catalysis provided by a combination of a source of bromine with one or more transition metal oxidation catalysts, more specifically cobalt, manganese or cobalt and manganese.
- acetic acid can be prepared by contacting a sufficient concentration of oxygen-containing gas (e.g., oxygen gas at at least 5 liters per hour per 100 grams of butane) with normal liquid butane in the presence of an acetic acid solution of components of catalysis consisting essentially of cobalt (e.g., 1 to 50 milliequivalents per mole of butane) and bromine (2 to 500 milliequivalents per mole of butane).
- oxygen-containing gas e.g., oxygen gas at at least 5 liters per hour per 100 grams of butane
- an acetic acid solution of components of catalysis consisting essentially of cobalt (e.g., 1 to 50 milliequivalents per mole of butane) and bromine (2 to 500 milliequivalents per mole of butane).
- cobalt e.g., 1 to 50 milliequivalents per mole of butane
- bromine e.g., 2,4-di
- Concentrated acetic acid (even glacial) distilled from the effluent produced by the foregoing liquid phase oxidation processes is contaminated with bromine-containing compounds and is not generally suitable as an article of commerce even though the commercial specification for glacial acetic acid or acetic anhydride do not set a maximum allowable value for bromine concentration.
- acetic acid becomes contaminated with bromides when used as solvent or reaction medium for the liquid phase oxidation of alkyl-substituted aromatic compounds (e.g., xylenes, toluene, trimethyl benzenes) with air to the corresponding aromatic carboxylic acids in the presence of catalysis provided by the components comprising a combination of one or more transition metal oxidation metal catalyst and a source of bromine (e.g., Br 2 , HBr, inorganic bromide salt, organic bromide such as tetrabromoethane).
- alkyl-substituted aromatic compounds e.g., xylenes, toluene, trimethyl benzenes
- a source of bromine e.g., Br 2 , HBr, inorganic bromide salt, organic bromide such as tetrabromoethane.
- the bromine contaminated acetic acid is treated by reaction with a metal having electrochemical potential between manganese and iron, inclusive and then contacting the acetic acid through an anion exchanger to remove the bromine or bromides.
- bromine contaminated acetic acids can contain both ionic and coordinate forms (e.g., bromine attached to carbon) of bromine which are not entirely removed by distillation or fractionation but rather carry through to the 97-100% acetic acid fraction in amounts of from 0.0005 up to 0.015 weight percent total of said two forms of bromine.
- ionic and coordinate forms e.g., bromine attached to carbon
- acetic acid can be purified to a bromine content below the present analytical detectability which is, on a weight basis, 3 parts bromine per 1 ⁇ 10 6 parts (i.e., 3 ppm) acetic acid.
- the foregoing removal of bromine to a concentration of less than 3 ppm bromine by weight on acetic acid can be accomplished by (a) contacting the concentrated (95 to 100%) acetic acid containing from 0.0005 up to 0.015 weight percent bromine and hydrogen gas with a palladium catalyst, preferably a palladium catalyst having palladium crystallites dispersed on the surface of activated carbon; and (b) then contacting the concentrated acetic acid with a solid absorbant.
- Such palladium on activated carbon (“Pd/C”) catalyst can have, on a weight basis, from 0.01 up to 1.0 percent palladium.
- the activated carbon should have a high surface area per unit of mass, desirably at least 800 m 2 /g and preferably 1000 to 3000 m 2 /g and a low extraneous metal content.
- the solid absorbant for example can be any one of the low metal content activated carbons or alumina.
- the step of contacting the bromine contaminated concentrated acetic acid and hydrogen with the Pd/C catalyst can be conducted with acetic acid in the liquid phase at a temperature of at least 50° C. or under vapor phase conditions at a temperature of at least 115° C.
- the liquid phase process is conducted by adding Br-contaminated concentrated acetic acid, particulate catalyst (2 to 20 mesh U.S. Standard Sieve) and hydrogen to a closed, pressure controlled vessel stirred zone at a temperature of from 50 up to 120° C. wherein the hydrogen partial pressure of from 0.35 up to 7 kg/cm 2 which will, at temperatures above 115° C., maintain the acetic acid in the liquid phase.
- the hydrogen-treated acetic acid can be withdrawn by decantation leaving the Pd/C catalyst in the reaction vessel or the suspension of Pd/C can be withdrawn through a filter.
- the liquid phase contacting also can be conducted by flow of acetic acid upward or downward through a fixed bed of Pd/C catalyst together with a hydrogen gas flow concurrent with or countercurrent to the flow of acetic acid through the fixed bed of Pd/C catalyst.
- the vapor phase contact of acetic acid and hydrogen with Pd/C catalyst can be conducted by mixing hydrogen gas at a partial pressure of 0.35 to 7 kg/cm 2 and vaporized (115° to 125° C.) concentrated acetic contaminated with bromine and passing the vapor-gas mixture upward or downward through a bed of Pd/C catalyst.
- the contacting of concentrated acetic acid with the solid absorbent can also be conducted with the acetic acid in the liquid or in the vapor phase.
- the liquid phase contacting with the solid absorbant can be carried out at a temperature of from about 20° up to 115° C. at 0 kg/cm gauge pressure or at a higher temperature and under elevated pressure to maintain acetic acid in the liquid phase.
- Such liquid phase contacting can be accomplished by a flow process wherein the liquid acetic acid is permitted to flow downward or upward through a fixed bed of particulated solid absorbant.
- the liquid acetic acid can be stirred with particulated solid absorbant and then separated by decantation, filtration, centrifugation or other means for solid-liquid separation.
- a single lot of bromine contaminated concentrated acetic acid (99 wt. % acetic acid) containing 58 ppm total of ionic and coordinate bromine is used in the following 5 examples, two of which are illustrative of the best mode of contact presently contemplated for the practice of the present invention.
- Ten milliliters of the 58 ppm bromine contaminated concentrated acetic acid are percolated through 1.0 gram of activated carbon of low metal content, i.e., 0.65 weight percent total metals.
- the recovered acetic acid is found by X-ray diffraction analysis to contain 41 ppm total ionic and coordinate bromine.
- Comparative Example III The process of Comparative Example III is repeated. After the 2 hours of stirring the acetic acid is separated from the Pd/C catalyst and divided into two equal volume portions. The first portion is percolated through 1.0 gram of activated alumina and is found by X-ray diffraction to contain thereafter less than 3 ppm total ionic and coordinate bromine. The second portion is percolated through the low metal content activated carbon described in Comparative Example II and is found by X-ray diffraction analysis thereafter to contain less than 3 ppm total ionic and coordinate bromine.
- the amount of Pd/C catalyst and the solid absorbants used in Illustrative Examples 1 and 2 are not the optimum with respect to the quantity of acetic acid therein used. However, one of ordinary skill in this art can readily determine the optimum Pd/C catalyst and absorbant to use per unit weight or volume of bromine contaminated concentrated acetic acid relative to the amount of total bromine contaminant therein to achieve the benefits of this invention as exemplified above.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Acetic acid of 95 to 100 weight percent strength containing ionic and coordinate bromide impurities can be purified to a bromine content of less than 3 ppm by the sequence of steps comprising catalytic hydrogenating said acetic acid, treating the hydrogenated acetic acid with a solid absorbant and separating acetic acid therefrom.
Description
This invention relates to the removal of bromine from acetic acid and more specifically pertains to the removal of bromine from acetic acid obtained by the catalytic liquid phase oxidation of butane in the presence of catalysis provided by a combination of a source of bromine with one or more transition metal oxidation catalysts, more specifically cobalt, manganese or cobalt and manganese.
According to the U.S. Pat. No. 3,293,292 it is essential for the preparation of acetic acid to use both manganese and cobalt (e.g., in their 2+ form acetate tetrahydrates) with a source of bromine (e.g., ammonium bromide) to oxidize butane with oxygen gas in the liquid phase at 176°-177° C. and a gauge pressure of 65.4 kg/cm2 in the presence of acetic acid as reaction solvent.
More recently U.S. Pat. No. 4,111,986 discloses that acetic acid can be prepared by contacting a sufficient concentration of oxygen-containing gas (e.g., oxygen gas at at least 5 liters per hour per 100 grams of butane) with normal liquid butane in the presence of an acetic acid solution of components of catalysis consisting essentially of cobalt (e.g., 1 to 50 milliequivalents per mole of butane) and bromine (2 to 500 milliequivalents per mole of butane). For this process reaction temperatures of at least 176°-177° C. are preferred at gauge pressures of from 35 up to 211 kg/cm2, preferably from 56 up to 105.5 kg/cm2.
Concentrated acetic acid (even glacial) distilled from the effluent produced by the foregoing liquid phase oxidation processes is contaminated with bromine-containing compounds and is not generally suitable as an article of commerce even though the commercial specification for glacial acetic acid or acetic anhydride do not set a maximum allowable value for bromine concentration.
Also acetic acid becomes contaminated with bromides when used as solvent or reaction medium for the liquid phase oxidation of alkyl-substituted aromatic compounds (e.g., xylenes, toluene, trimethyl benzenes) with air to the corresponding aromatic carboxylic acids in the presence of catalysis provided by the components comprising a combination of one or more transition metal oxidation metal catalyst and a source of bromine (e.g., Br2, HBr, inorganic bromide salt, organic bromide such as tetrabromoethane). While some who practice such process for the production of aromatic carboxylic acids reuse the bromine-contaminated acetic acid in the oxidation process, others (e.g., the assignee of U.S. Pat. No. 3,578,706) prefer to remove the bromine or bromine-containing contaminants before resuing the acetic acid in the oxidation process.
According to said U.S. Pat. No. 3,578,706, the bromine contaminated acetic acid is treated by reaction with a metal having electrochemical potential between manganese and iron, inclusive and then contacting the acetic acid through an anion exchanger to remove the bromine or bromides.
Such bromine contaminated acetic acids can contain both ionic and coordinate forms (e.g., bromine attached to carbon) of bromine which are not entirely removed by distillation or fractionation but rather carry through to the 97-100% acetic acid fraction in amounts of from 0.0005 up to 0.015 weight percent total of said two forms of bromine. We have found that by a single two step process the concentrated acetic acid can be purified to a bromine content below the present analytical detectability which is, on a weight basis, 3 parts bromine per 1×106 parts (i.e., 3 ppm) acetic acid.
The foregoing removal of bromine to a concentration of less than 3 ppm bromine by weight on acetic acid can be accomplished by (a) contacting the concentrated (95 to 100%) acetic acid containing from 0.0005 up to 0.015 weight percent bromine and hydrogen gas with a palladium catalyst, preferably a palladium catalyst having palladium crystallites dispersed on the surface of activated carbon; and (b) then contacting the concentrated acetic acid with a solid absorbant.
Such palladium on activated carbon ("Pd/C") catalyst can have, on a weight basis, from 0.01 up to 1.0 percent palladium. The activated carbon should have a high surface area per unit of mass, desirably at least 800 m2 /g and preferably 1000 to 3000 m2 /g and a low extraneous metal content.
The solid absorbant, for example can be any one of the low metal content activated carbons or alumina.
The step of contacting the bromine contaminated concentrated acetic acid and hydrogen with the Pd/C catalyst can be conducted with acetic acid in the liquid phase at a temperature of at least 50° C. or under vapor phase conditions at a temperature of at least 115° C. The liquid phase process is conducted by adding Br-contaminated concentrated acetic acid, particulate catalyst (2 to 20 mesh U.S. Standard Sieve) and hydrogen to a closed, pressure controlled vessel stirred zone at a temperature of from 50 up to 120° C. wherein the hydrogen partial pressure of from 0.35 up to 7 kg/cm2 which will, at temperatures above 115° C., maintain the acetic acid in the liquid phase. The hydrogen-treated acetic acid can be withdrawn by decantation leaving the Pd/C catalyst in the reaction vessel or the suspension of Pd/C can be withdrawn through a filter. The liquid phase contacting also can be conducted by flow of acetic acid upward or downward through a fixed bed of Pd/C catalyst together with a hydrogen gas flow concurrent with or countercurrent to the flow of acetic acid through the fixed bed of Pd/C catalyst.
The vapor phase contact of acetic acid and hydrogen with Pd/C catalyst can be conducted by mixing hydrogen gas at a partial pressure of 0.35 to 7 kg/cm2 and vaporized (115° to 125° C.) concentrated acetic contaminated with bromine and passing the vapor-gas mixture upward or downward through a bed of Pd/C catalyst.
The contacting of concentrated acetic acid with the solid absorbent can also be conducted with the acetic acid in the liquid or in the vapor phase. The liquid phase contacting with the solid absorbant can be carried out at a temperature of from about 20° up to 115° C. at 0 kg/cm gauge pressure or at a higher temperature and under elevated pressure to maintain acetic acid in the liquid phase. Such liquid phase contacting can be accomplished by a flow process wherein the liquid acetic acid is permitted to flow downward or upward through a fixed bed of particulated solid absorbant. Or the liquid acetic acid can be stirred with particulated solid absorbant and then separated by decantation, filtration, centrifugation or other means for solid-liquid separation.
A single lot of bromine contaminated concentrated acetic acid (99 wt. % acetic acid) containing 58 ppm total of ionic and coordinate bromine is used in the following 5 examples, two of which are illustrative of the best mode of contact presently contemplated for the practice of the present invention.
Ten milliliters of the 58 ppm bromine contaminated bromine is percolated through 1.0 gram of activated alumina at a temperature between 20° and 22° C. By X-ray diffraction analysis the acetic acid recovered is found to contain 54 ppm total of ionic and coordinate bromine.
Ten milliliters of the 58 ppm bromine contaminated concentrated acetic acid are percolated through 1.0 gram of activated carbon of low metal content, i.e., 0.65 weight percent total metals. The recovered acetic acid is found by X-ray diffraction analysis to contain 41 ppm total ionic and coordinate bromine.
Five grams of the 58 ppm bromine contaminated concentrated acetic acid are charged to a Fisher-Porter Bottle together with 5.0 grams of 4×8 mesh (U.S. Standard Sieve) Pd/C particulate catalyst having a Pd crystallite content of 0.5 weight percent on 1100 m2 /g surface area to mass activated carbon. The bottle is charged with hydrogen to a gauge pressure of 1.75 kg/cm2 and heated by a water bath to 100° C. for 2 hours while the bottle's contents are stirred. The acetic acid so treated is separated from the catalyst and is analyzed by X-ray diffraction. The recovered acetic acid is found to contain 20 ppm total ionic and coordinate bromine.
The process of Comparative Example III is repeated. After the 2 hours of stirring the acetic acid is separated from the Pd/C catalyst and divided into two equal volume portions. The first portion is percolated through 1.0 gram of activated alumina and is found by X-ray diffraction to contain thereafter less than 3 ppm total ionic and coordinate bromine. The second portion is percolated through the low metal content activated carbon described in Comparative Example II and is found by X-ray diffraction analysis thereafter to contain less than 3 ppm total ionic and coordinate bromine.
The amount of Pd/C catalyst and the solid absorbants used in Illustrative Examples 1 and 2 are not the optimum with respect to the quantity of acetic acid therein used. However, one of ordinary skill in this art can readily determine the optimum Pd/C catalyst and absorbant to use per unit weight or volume of bromine contaminated concentrated acetic acid relative to the amount of total bromine contaminant therein to achieve the benefits of this invention as exemplified above.
Claims (5)
1. The method of removing bromine from acetic acid of 95 to 100 weight percent concentration contaminated with ionic and co-ordinate bromine in a total amount of from 0.0005 to 0.015 weight percent by contacting hydrogen and said contaminated acetic acid with a palladium catalyst having Pd crystallites dispersed on the surface of low extraneous metal content activated carbon having a surface area to unit mass ratio of at least 800 m2 /g, separating the acetic acid from the catalyst, contacting the separated acetic acid with a solid absorbant, and separating acetic acid from the absorbant.
2. The method of claim 1 wherein the palladium catalyst is contacted with the contaminated acetic acid in the vapor phase and the absorbant is contacted with a vapor phase of acetic acid.
3. The method of claim 1 wherein the palladium catalyst in particulate form is contacted with the contaminated acetic acid in the liquid phase and thereafter the liquid acetic acid is contacted with particulate solid absorbant.
4. The method of claim 3 wherein the palladium catalyst contains 0.5 weight percent palladium and the solid absorbant is activated alumina.
5. The method of claim 3 wherein the palladium catalyst contains 0.5 weight percent palladium and the solid absorbant is low metal content activated carbon.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US05/970,226 US4228307A (en) | 1978-12-18 | 1978-12-18 | Removal of bromine from acetic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/970,226 US4228307A (en) | 1978-12-18 | 1978-12-18 | Removal of bromine from acetic acid |
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US4228307A true US4228307A (en) | 1980-10-14 |
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US05/970,226 Expired - Lifetime US4228307A (en) | 1978-12-18 | 1978-12-18 | Removal of bromine from acetic acid |
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